Polyhalo disulfide alcohols and derivatives

ABSTRACT

Compounds are prepared having one of the formulae   AND

United States Patent wi Emerson et al.

[4 1 Sept. 18, 1973 POLYHALO DISULFIDE ALCOHOLS AND DERIVATIVES [75]Inventors: Carl D. Emerson, Kansas City, Mo.;

Paul C. Aichenegg, Prairie Village,

Kans.

[73] Assignee: Chemagro Corporation, Kansas City,

[22] Filed: Sept. 9, 1969 [21] Appl. No.: 856,501

[60] Related U.S. Application Data Division or Ser. No. 757,487, Sept.4, 1968, Pat. No. 3,641,109, which is a Continuation-impart of Ser. No.560,125,.Iune 24, l966.abandoned.

[1966 Aichenegg et al. 260/608 Primary Exaniiner-Lewis Gotts AssistantExaminer-D. R. Phillips Attorn'ey-Cushman, Darby & Cushman [57] ABSTRACTCompounds are prepared having one of the formulae 1 H n-sscmonon won and

(2) B-SSCH,CH,Ol-l where A is di to tetrahaloethyl or di to trihalovinyland B is di to trihalovinyl and all halogen atoms have an atomic weightof 35 to 80. The compounds are useful as fungicides, desiccants andnematocides and to some extent as herbicides.

11 Claims, No Drawings POLYHALO DISULFIDE ALCOHOLS AND DERIVATIVES Thisapplication is a division of Ser. No. 757,487, filed Sept. 4, 1968, nowUS. Pat. No. 3,641,109 which application is a" continuation-in-part ofSer. No. 560,125, filed June 24, 1966, now abandoned.

The present invention relates to novel polyhalo disulfide alcohols andderivatives thereof.

It is an object of the present invention t prepare novel polyhalo ethylor vinyl disulfide alcohols and derivatives thereof. I

Another object is to prepare novel polyh'alo'ethyl or vinyl dithioethylchloroformategroup containing organic compounds which are useful asintermediates in making other compounds.

A further object is to prepare novel fungicides.

An additional object is to prepare novel nematocides.

Yet another object is to prepare, novel defoliants and desiccants.

A still further object is to prepare post emergent herbicides.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should, be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be at tained by preparing acompound having one of the following formulae:

(1) ""asscnie'n'bfi; B

2 f ASSCHgCHOQQnRH (a) (Asscmcinono =x;

4 7 x Rz asscmpnoo-u E Ba A A s scmcfiocQ,

and

(6) A s s cmcinK where A is selected from the group consisting of di totetrahaloethyl and di to trihalovinyl;

B is selected from the group consisting of hydrogen and CH Ol-l D ishydrogen or crnoc'iotnm;

E is hydrogen or G is hydrogen or with the proviso that not'more thanone of R and R,

is hydrogen and collectively with the adjacent nitrogen atom form a 5 to6 membered heterocyclic ring having up to, 1 oxygen atom therein;

R is R, or

or phenyl ethylene or phenoxymethyl having up to 3 halogen atoms and upto 1 methyl group on the aromatic ring;

O O ll' a- K15 O (CH2)mCO-\] or O CHCHCO-J or loan 06 oli where J ishydrogen or, ASSCH CH m is an integer from O to 2 inclusive and allhalogen atoms in the compounds have an atomic weight of 35 tov 80, Le.are chlorine or bromine.

Preferably all halogen atoms are chlorine and preferably any alkyl groupis a lower alkyl group, most preferably having 1 to 4 carbon atoms. Thepreferred compounds are those where A is trichloroethyl ordichlorovinyl.

The compounds of the present invention are useful as fungicides,nematocides, defoliants and desiccants, e.g. for cotton and, beans, postemergent herbicides, preemei'gent herbicides, bactericides, etc.

The compounds of formula (1 also are useful in preparing the compoundsof formulae (2), (3), (4), (5) and (6) and other compounds.

The compounds of formula (5) are useful in preparing the compounds offormula (2) which are carbonates or thiol cabonates and as intermediatesin making other compounds.

The compounds of formula (1) are prepared by reacting the correspondingsulfenyl halides with the appropriate mercapto alcohol. As sulfenylhalides there can be used 1,2,2-trichloroethyl sulfenyl chloride,2,2,2-trichloroethyl sulfenyl chloride, 2,2- dichloroethyl sulfenylchloride, l,2-dichloroethyl sulfenyl chloride, l,2,2,2-tetrachloroethylsulfenyl chloride, 1,2,2-tribromoethyl sulfenyl chloride, 2,2-dichlorovinyl sulfenyl chloride, l,2-dichlorovinyl sulfenyl chloride,2,2-dibromovinyl sulfenyl bromide, l,2,2-trichlorovinyl sulfenylchloride.

As the mercaptoalcohol there can be used Z-mercaptoethanol ormonothioglycerol (3-mercapto-l,2-dihydroxypropane).

The unsaturated halodisulfide alcohols of formula l) can also beprepared by dehydrohalogenation of the appropriate polyhaloethylB-hydroxyethyl disulfide. Examples of compounds within formula (1) are1,2,2- trichloroethyl-B-hydroxyethyl disulfide, 2,2,2-trichloroethyl-B-hydroxyethyl disulfide, 1 ,2,2-trichloroethyl-2',3-dihydroxypropyl disulfide, 2,2,2-trichloroethyl-2',3-dihydroxypropyl disulfide, 2,2-dichlorovinyl-B-hydroxyethyl disulfide, 2,2-dichlorovinyl-2',3-dihydroxypropyl disulfide, l,2,2,2-

tetrachloroethyl-B-hydroxyethyl disulfide, 2,2-dichloroethyl-B-hydroxyethyl disulfide, l ,2,2-trichlorovinyl-B-hydroxyethyl disulfide, 1 ,2,2,2-

tetrachloroethyLZ',3'-dihydroxypropyl disulfide, 1,2-dichloroethyl-2',3-dihydroxypropyl disulfide, 1,2-dichlorovinyl-B-hydroxyethyl disulfide, l ,2,2-trichlorovinyl-2',3'-dihydroxypropyl disulfide, 1,2,2-tribromoethyl-B-hydroxyethyl disulfide, 2,2- dibromovinyl-fihydroxyethyl disulfide, 2,2,2- tribromoethyl-'2,3-hydroxypropyldisulfide and 2,2- dibromovinyl-Z,3'-dihydroxypropyl disulfide.

The compounds of formula (2) which are esters (other than carbonates,thiol carbonates and dithiocarbonates) are prepared by reacting an acylhalide, e.g. an acyl chloride or acyl bromide, with the appropriatealcohol of formula (I). 7

Examples of suitable acyl halides are acetyl chloride, chloroacetylchloride, acetyl bromide, dichloroacetyl chloride, trichloroacetylchloride, propionyl chloride, butyryl chloride, valcryl chloride,caproyl chloride, caprylyl chloride, benzoyl chloride, p-chlorobenzoylchloride, 2,4-dichlorobenzoyl chloride, 2,4,5- trichlorobenzoylchloride, toluyl chloride, 2- butylbenzoyl chloride, cinnamoyl chloride,2-methyl-4- chlorobenzoyl chloride, m-bromobenzoyl 'bromide, a-naphthoylchloride, B-naphthoyl chloride, B-methyl a-naphthoyl chloride,chloropropionyl chloride,

2,4-dichlorophenoxyacetyl chloride, 2,4,5,-trichloro-' phenoxyacetylchloride, 2-methyl-4-chlorophenoxyacetyl chloride,2-methyl-4-bromophenoxyacetyl chloride, 2,4,5-tribromophenoxyacetylchloride, 2,4- dichloro-S-bromophenoxyacetyl chloride.

Examples of esters within formula (2) are 1,2,2- trichloroethyldithioethyl acetate, 2,2,2-trichloroethyl dithioethyl acetate,2,2-dichlorovinyl dithioethyl acetate,l,2,2-trichloroethyl-2Q3-diacetoxypropyl disulfide,2,2,2-trichloroethyl-2',3Qdiacetoxypropyl disulfide, 2,2-dichlorovinyl-2,3' -di acetoxypropyl disulfide, l,2-dichlorovinyl-2,3-diacetoxypropyldisulfide, 1,2-

. 2,2,2-trichloroethyl-2',3-dipropionoxypropyltrichlorovinyl-2,3'-diacetoxypropyl I disulfide, 1,2,2-

tribromoethyl dithioethyl acetate, 2,2-dibromovinyl dithioethyl acetate,2 ,2,2-tribromoethyl-2 ,3 diacetoxypropyl disulfide,1,2,2-trichloroethyl' dithioethyl propionate, 2,2,2-trichloroethyldithioethyl propionate, 2,2-dichlorovinyl dithioethyl propionate, l,2,-2-trichloroethyl-2',3'-dipropionoxy-propyl disulfide,

disultide, 2,2-dichlorovinyl-2',3'-dipropionoxypropyl disulfide,l,2,2-trichloroethyl-dithioethyl butyrate, 2,2,2- trichloroethyldithioethyl butyrate, 2,2-dichlorovinyl dithioethyl butyrate,1,2,2-trichlorovinyl dithioethyl butyrate, l ,2,2-trichloroethyl-2',3'-dibutyryloxypropyl disulfide, 2,2-dichlorovinyl-2,3-dibutyryloxypropyldisulfide, 2,2,2-trichloroethyl dithioethyl valerate,1,2,2-trichloroethyl dithioethyl decanoate, 2,2- dichlorovinyldithioethyl caprylate, l ,2 ,2- trichloroethyl-2 ,3'-didecanoyloxypropyl disulfide 1,2,2-trichloroethyl dithioethylchloroacetate, 2,2,2-

trichloroethyl dithioethyl chloroacetate 2 ,2- dichlorovinyl dithioethylchloroacetate, l ,2 ,2- trichloroethyl-2',3-di(chloroacetyloxy)propyldisulfide, 2,2-dichlorovinyl-2',3'-di(chloroacetyloxy)propyl disulfide,1,2,2-trichloroethyl dithioethyl dichloroacetate, 2,2-dichlorovinyldithioethyl trichloroacetate, 2,-2,2-trichloroethyl-2',3'-di(trichloroacetyloxy) propyl disulfide,1,2,2-trichloroethyl dithioethyl benzoate, 2,2,2-trichloroethyldithioethyl benzoate, l,2,2,2-tetrachloroethyl dithioethyl benzoate,2,2-dichlorovinyl dithioethyl benzoate, 2,2,2-tribromoethyl dithioethylbenzoate, l,2,2-trichloroethyl-2',3 '-dibenzoyloxypropyl disulfide,2,2,2-trichloroethyl-2',3'-dibenzoyloxypropyl disulfide,2,2-dichlorovinyl-2',3'-dibenzoyloxypropyl disulfide,1,2,2-trichloroethyl dithioethyl 4- chlorobenzoate, 2,2-dichlorovinyldithioethyl 2,4- dichlorobenzoate, 2,2,2-trichloroethyl dithioethyl2,4,5-trichlorobenzoate, 1,2,2-trichloroethyl dithioethyl2,4,5-trichlorophenoxyacetate, 2,2-dichlorovinyl dithioethyl2,4-dichlorophenoxyacetate, 2,2,2- trichloroethyl-2 ,3 '-di( 2' ,4' ,5'-trichlorobenzoylox y)propyl disulfide, 1,2,2-trichloroethyldithioethyl 4- butylbenzoate, 2,2,2-trichloroethyl dithioethyl2'-methyl-4'-chlorobenzoate, 2,2-dichlorovinyl dithioethyl cinnamate,l,2,2-trichloroethyl-2',3-di(cinnamoyloxyl)propyl disulfide,2,2,2-trichloroethyl dithioethyl a-naphthoate, 2,2-dichlorovinyldithioethyl B-naphthoate, l,2,2-trichloroethyl dithioethyl a-methylB-naphthoate, 2,2-dichlorovinyl-2,3'-dia-naph thoyloxypropyl disulfide,1,2,2-tribromoethyl dithioethyl 4-bromobenzoate, l ,2 ,2-trichloroethyldithioethyl-Z-methyl-4'- chlorophenoxyacetate,2,2,2-triehloroethyldithioethyl- 2-methyl-4chlorophenoxyacetate, 2,2-dichlorovinyldithioethyl-Z'-methyl-4'- chlorophenoxyacetate,1,2,Z-tribromoethyldithioethyl- 2-methyl-4'-bromophenoxyacetate, 2,2,2-trichloroethyldithioethyl 2,4,5-trichlorophenoxyacetate,2,2-dichlorovinyl 2,4,5-trichlorophenoxyacetate,

l ,2,2-trichloroethyldithioethy] 2 ,4- dichlorophenoxyacetate,2,2,2-trichloroethyldithioethyl 2,4-dichlorophenoxyacetate, l ,2 ,2-trichloroethyldithioethyl trichloroacetate, l ,2 ,2-trichloroethyldithioethyl cinnamate, l ,2,2 -trichloroethyldithioethylphenoxyacetate sulfide, 2,2-dichlorovinyl-2',3 '-di (2",4' ',5-trichlorophenoxyacetyloxy) propyl disulfide, l,2,2-trichloroethyl-2,3'-di (2"-methyl-4"- chlorophenoxyacetyloxy) propyl disulfide,2,2,2-trichloroethyl-2,3 '-di (2"-methyl-4- chlorophenoxyacetyloxy)propyl disulfide, 2,2- dichlorovinyl-2',3 -di (2-methyl-4"-chlorophenoxyacetyloxy) propyl disulfide, 1,2-dichlorovinyldithioethyl-2-methyl-4- chlorophenoxyacetate, l,2,2,2-tetrachloroethyldithioethyl-2-methyl-4- chlorophenoxyacetate, l,2,2,2-

tetrachloroethyldithioethyl-2,4- dichlorophenoxyacetate,l,2,2,2-tetrachloroethyldithioethyl 2, 4, -trichlorophenoxyacetate.

The compounds of formula (2) which are carbonates, thiol carbonates anddithiocarbonates are made by one of the following three methods:

II (a) reacting the appropriate alcohol of formula (1) with theappropriate alkyl or aryl chloroformate;

II (b) reacting the appropriate disulfide chloroformate of formula (5)with the appropriate alkyl alcohol, aryl alcohol, phenol or mercaptan orxanthate.

ll (c) reacting the appropriate polyhaloethyl or polyhalovinyl sulfenylhalide, e.g. any of those previously set forth, with amercaptocarbonate.

Examples of suitable chloroformates for reaction I] (a) are methylchloroformate, ethyl chloroformate, propyl chloroformate, butylchloroformate, isobutyl chloroformate, hexyl chloroformate, cyclohexylchloroformate, octyl chloroformate, dodecyl chloroformate, phenylchloroformate, 4-methylphenyl chloroformate, 4-chlorophenylchloroformate, a-naphthyl chloroformate, B-naphthyl chloroformate, 2-bromophenyl chloroformate, Z-chloroethyl chloroformate, 3-butylphenylchloroformate, methyl chlorothiol formate, ethyl chlorothiol formate,isopropyl chlorothiol formate, butyl chlorothiol formate, amylchlorothiol formate, phenyl chlorothiol formate, 2,4- dimethylphenylchlorothiol formate, B-naphthyl chlorothiol formate.

Examples of suitable alcohols, phenols, mercaptans and xanthates for usein reaction II (b) are methyl alcohol, ethyl alcohol, isopropyl alcohol,propyl alcohol, butyl alcohol, sec. butyl alcohol amyl alcohol,cyclohexyl alcohol, hexyl alcohol, octyl alcohol, isooctyl alcohol,dodecyl alcohol, phenol, m-cresol, o-cresol, pcresol, benzyl alcohol,p-chlorophenol, a-napthol, ,B-naphthol, a-methyl-B-naphthol, methylmercaptan, ethyl mercaptan, propyl mercaptan, dodecyl mercaptan, butylmercaptan, cyclohexyl mercaptan, amyl mercaptan, benzyl mercaptan,thiophenol, p-thiocresol, a-naphthyl mercaptan, ethylene chloohydrin,propylene chlorohydrin, potassium ethyl xanthate, sodium ethyl xanthate,potassium butyl xanthate, potassium methyl xanthate. The disulfidechloroformates which can be employed are set forth infra.

Examples of suitable mercaptocarbonates for reaction II (c) areethyI-Z-mercaptoethyl carbonate, methyI-Z-mercaptoethyl carbonate,propyl-2-mercaptoethyl carbonate, butyl-2-mercaptoethyl carbonate,

hexyl-2-mercaptoethyl carbonate, cyclohexyl-Z-mercaptoethyl carbonate,phenyl-2-mercaptoethyl carbonate, p-tolyl-2-mercaptoethyl carbonate,a-naphthyl-2-mercaptoethyl carbonate.

Examples of carbonates, thiol carbonates and dithiocarbonates withinformula (2) are l,2,2,-trichloroethyl dithioethyl-ethyl carbonate,2,2,2-trichloroethyl dithioethyl-ethyl carbonate, l,2,2-trichloroethyldithioethylphenyl carbonate, 2,2,2-trichloroethyl dithioethylphenylcarbonate, 2,2-dichlorovinyl dithioethyl-ethyl carbonate,2,2-dichlorovinyl dithioethyl-phenyl carbonate, l,2,2,2-tetrachloroethyldithioethyl-ethyl carbonate l,2,2-trichlorovinyl dithioethyl-ethylcarbonate, 2,2,2-tribromoethyl dithioethyl-ethyl carbonate,2,2-dibromovinyl dithioethyl-phenyl carbonate, l,2- dichloroethyldithioethyl-ethyl carbonate, l,2,2-

trichloroethyl dithioethyl-methyl carbonate, 2,2,2- trichloroethyldithioethyl-ethyl carbonate, 1 ,2- dichlorovinyl dithioethyl-m ethylcarbonate, 2 ,2- dichlorovinyl dithioethyl-methyl carbonate, 2 ,2 ,2-trichloroethyl dithioethyl-propyl carbonate, 1 ,2,2- trichloroethyldithioethyl-isopropyl carbonate, 2,2- dichlorovinyl dithioethyl-propylcarbonate l ,2 ,2- trichloroethyl dithioethyl-butyl carbonate, 2,2,2-trichloroethyl dithioethyl-butyl carbonate, 2,2- dichlorovinyldithioethyl-butyl carbonate, l ,2,2-

trichloroethyl dithioethyl sec. butyl carbonate, 2,2,2-

trichloroethyl dithioethyl-amyl carbonate, 2,2- dichlorovinyldithioethyl-amyl carbonate, 1 ,2,2- trichloroethyl dithioethyl-hexylcarbonate 2 ,2-

dichlorovinyl dithioethylcyclohexyl carbonate, 2,2,2- trichloroethyldithioethyl-cyclohexyl carbonate, 1,2,2- trichloroethyldithioethyl-octyl carbonate, 2,2,2- trichloroethyl dithioethyl-dodecylcarbonate, 2,2- dichlorovinyl dithioethyl-dodecyl carbonate, 1 ,2,2-trichloroethyl dithioethyl-p-tolyl carbonate, 2,2,2- trichloroethyldithioethyl-o-tolyl carbonate, 2,2-

dichlorovinyl dithioethyl-m-tolyl carbonate, l,2,2-

trichloroethyl dithioethyl-p-butylphenyl carbonate, 2,2,2-trichloroethyldithioethyl-B-naphthyl carbonate, 2,2-dichlorovinyldithioethyl-a-naphthyl carbonate, l,2-,2-trichloroethyldithioethyl-Z'-chloroethyl carbonate, l,2,2-trichloroethyldithioethyl-p-chlorophenyl carbonate, 2,2,2-tribromoethyldithioethyl-obromophenyl carbonate, 2,2-dichlorovinyldithioethylm-chlorophenyl carbonate, 2,2,2-trichloroethyldithioethyl-2',45-trichlorophenyl carbonate, 2,2- dichlorovinyldithioethyl-2'-methyl-4'-chlorophenyl carbonate, 1 ,1 ,2-trichloro-3,4-dithiaheptane-6,7-di (ethyl carbonate), 1 ,1 l-trichloro-3,4-dithiaheptane- 6,7-di (methyl carbonate), 1, l-dichloro-3 ,4- dithiaheptane-l,6,7-di (ethyl carbonate), l,l,2-trichloro-3,4-dithiaheptane-6,7-di (propyl carbonate), 1 ,l,1-trichloro-3,4-dithiaheptane-6,7-di (butyl carbonate), 1, l-dichloro-3,4-dithiaheptanel ,6,7-di (propyl carbonate), 1 ,l,2-trichloro-3,4-dithiaheptane-6,7-di (phenyl carbonate), l,l,2-trichloro-3,4-dithiaheptane- 6,7-di phenyl carbonate), 1, l-dichloro-3 ,4- dithiaheptane-l,6,7-di (phenyl carbonate),l,ldichloro-3,4-dithiaheptane-l,6,7-di (a-naphthyl carbonate),l,l,l-trichloro-3,4-dithiaheptane -6,7-di (pchlorophenyl carbonate),l,2,2-trichloroethyl dithioethyl-S-ethyl thiol carbonate,2,2,2trichloroethyl dithioethyl-S-ethyl thiol carbonate,2,2-dichlorovinyl dithioethyl-S-ethyl thiol carbonate, 2,2,2-tribromoethyl dithioethyl-S-ethyl thiol carbonate, 2,2- dibromovinyldithioethyl-S-ethyl thiol carbonate,

1,2,2-trichloroethyl dithioethyl-S-methyl thiol carbonate,2,2-dichlrovinyl dithioethyl-S-methyl thiol carbonate,2,2,2-trichloroethyl dithioethyl-S-propyl thiol carbonate,l,2,2-trichlorovinyl dithioethyl-S-amyl thiol carbonate,l,2,2,2-tetrachloroethyl dithioethyl-S-hexyl thiol carbonate,l,2,2-trichloroethyl dithioethyl-S- butyl thiol carbonate,2,2,2-trichloroethyl dithioethyl- S-butyl thiol carbonate,2,2-dichlorovinyl dithioethyl- S-butyl thiol carbonate,1,2,2-trichloroethyl dithioethyl-S-octyl thiol carbonate,l,2,2-trichloroethyl dithioethyl-S-phenyl thiol carbonate, 2,2,2-trichloroethyl dithioethyl-S-phenyl thiol carbonate, 2,2-dichlorovinyldithioethyl-S-phenyl thiol carbonate, l,2,2-trichloroethyldithioethyl-S-o-tolyl thiol carbonate, 2,2-dichlorovinyldithioethyl-S-p-tolyl thiol carbonate, 2,2,2-trichloroethyldithioethyl-e-a-napthyl thiol carbonate, 2,2-dichlorovinyldithioethyl-S-2,4- dichlorophenyl thiol carbonate, 2,2-dichlorovinyldithioethyl-S-2'-chloroethyl thiol carbonate, 1,1,2-trichloro-3,4-dithiaheptane-6,7-di (ethyl thiol carbonate),l,1,l-trichloro-3,4-dithiaheptane -6,7-di (ethyl thiol carbonate), 1 l-dichloro-3,4-dithiaheptanel ,6,7- di (ethyl thiol carbonate),l,l,l-trichloro-3,4- dithiaheptane-6,7-di (methyl thiol carbonate),l,ldichloro-3,4-dithiaheptane-l,6,7-di (methyl thiol carbonate l, l l-trichloro-3 ,4-dithiaheptane-6,7-di (butyl thiol carbonate),l,l-dichloro-3,4- dithiaheptane-l,6,7-di (Butyl thiol carbonate), 1,1,1-trichlor0-3,4-dithiaheptane-6,7-di (phenyl thiol carbonate),l,l-dichloro-3,4-dithiaheptene-l,6,7-di (phenyl thiol carbonate), 1, l,2-trichloro-3,4-dithiaheptane- 6,7-di (2'-chloro 4'-methylphenyl thiolcarbonate), 1,- l-dichloro-3,4-dithiaheptene(-l )6,7-di (B-naphthylthiol carbonate), l,2,2-trichloroethyl dithioethyl-S- ethyl dithiocarbonate, 2,2,2-trichloroethyl dithioethyl- S-ethyl dithio carbonate,2,2-dichlorovinyl dithioethyl- S-ethyl dithio carbonate,l,2-dichlorovinyl dithioethyl- S-ethyl dithio carbonate,2,2,2-tribromoethyl dithioethyl-S-ethyl dithio carbonate,2,2-dibromovinyl dithioethyl-S-ethyl dithio carbonate, 1 ,2,2-trichloroethyl dithioethyl-S-methyl dithio carbonate, 2,2-dichlorovinyldithioethyl-S-methyl dithio carbonate, 2,2-trichloroethyldithioethyl-S-propyl dithio carbonate, l,2,2-trichlorovinyldithioethyl-S-heptyl dithio carbonate, l,2,2,2-tetrachloroethyldithioethyl-S-hexyl dithio carbonate, 1,2,2-trichloroethyldithioethyl-S- butyl dithio carbonate, 2,2,2-trichloroethyl dithioethyl-S-butyl dithio carbonate, 2,2-dichlorovinyl dithioethyl S-butyl dithiocarbonate, 1,2,2-trichloroethyl dithioethyl-S-octyl dithio carbonate,1,2,2-trichloroethyl-S- phenyl dithio carbonate, 2,2,2-trichloroethyldithioethyl-S-phenyl dithio carbonate, 2,2-dichlorovinyl dithioethyl-S-phenyl dithio carbonate, 1,2,2-trichloroethyldithioethyl-S-p-tolyl dithio carbonate, 2,2- dichlorovinyldithioethyl-S-o-tolyl dithio carbonate, 2,2,2-trichloroethyldithioethyl-S-a-naphthyl dithio carbonate, 2,2-dichlorovinyldithioethyl-S-2,4- dichlorophenyl dithio carbonate, 2,2-dichlorovinyldithioethyl-S-2-chloroethyl dithio carbonate, 1,1,2-trichloro-3,4-dithiaheptane-6,7-di (ethyl dithio carbonate), 1 l l-trichloro-3 ,4-dithia-heptane-6,7-( ethyl dithio carbonate) 1 l-dichloro-3,4-dithiaheptene(-l -6,7-di (ethyl dithio carbonate),1,l-trichloro-3,4- dithiaheptane-6,7-di (methyl dithio carbonate), 1,1-dichloro-3,4-dithiaheptanel ,6,7-di (methyl dithio carbonate l l,1-trichloro-3 ,4-dithiaheptane-6,7-di

(butyl dithio carbonate), l,l-dichloro-3,4-dithiaheptene-l,6,7-di (butyldithio carbonate), 1,1,1- trichloro-3,4dithiaheptane-6,7-di(phenyldithio carbonate), l l -dichloro-3,4-dithiaheptene-l ,6,7-di (phenyldithio carbonate), 1 ,2-trichloro-3 ,4- dithiaheptane-6,7-di(2-chloro-4'-methylphenyl dithio carbonate), 1 l -dichloro-3,4-dithiaheptene-l ,6,7-di (a-naphthyl dithio carbonate).

O[B-(l,2,2-trichloroethyl dithio) ethyll-S-[O-ethylthiocarboxyl] dithiocarbonate, O-[B-(2,2,2- trichloroethyl dithio) ethyl]S-[O-methyl-thiocarboxyl] dithio carbonate, O-[B-(2,2-dichlorovinyl dithio)ethyl]-S-[O-butyl-thiocarboxyl] dithio carbonate,0-[/3-(l,2,2,-trichloroethyl dithio) ethyl]-S-[O- phenyl-thiocarboxyl]dithio carbonate, 0-[B-(2,2- dichlorovinyl dithio)ethyl]-S-[O-phenyl-thiocarboxyl] dithio carbonate, 0-[B-(1,2,2-trichloroethyl dithio )ethyl]-S-[O-p-tolyLthiocarboxyl] dithiocarbonate.

The compounds of formula (3) are made by reacting the appropriatealcohol of formula (1) with the appropriate disulfide chloroformate offormula (5).

Examples of compounds within formula (3) are bis-( l,2,2-thiochloroethyldithioethyl) carbonate, bis-(2,2,2-trichloroethyl dithioethyl)carbonate, bis- (2,2-dichlorovinyl dithioethyl) carbonate 2-trichloroethyl dithioethyl)-(2,2-dichlorovinyl dithioethyl) carbonate,bis (1,2,2-tribromoethyl dithioethyl) carbonate, bis(1,2,2-trichloroethyl dithioethyl) thiocarbonate, bis (2,2-dichlorovinyldithioethyl) thiocarbonate.

The compounds of formula (4) are made by one of the following methods:

III (a) reacting the appropriate alcohol of formula (1) with theappropriate alkyl, aryl or haloaryl isocyanate or isothiocyanate;

III (b) by reacting the appropriate alcohol of formula (1) with anappropriate carbamoyl halide, e.g. chloride or bromide;

[II (c) by reacting the appropriate polyhaloethyl or polyhalovinyldisulfide chloroformate of formula (5) with the appropriate amount of aprimary or secondary amine. 2 equivalents of amine are required for eachequivalent of chloroformate.

Examples of suitable isocyanates for reaction III (a) are phenylisocyanates p-tolyl isocyanate, m-tolyl isocyanate, a-naphthylisocyanate, 2-chlorophenyl isocyanate, 2,4-dichl0rophenyl isocyanate,ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate,cylcohexyl isocyanate, dodecyl isocyanate, 2-methyl-4- chlorophenylisocyanate, phenyl isothiocyanate, o-tolyl isothiocyanate, ethylisothiocyanate, methyl isothiocyanate, butyl isothiocyanate, B-naphthylisothiocyanate.

Examples of suitable carbamoyl halides for reaction II] (b) are dimethylcarbamoyl chloride, diethyl carbamoyl chloride, diethyl carbamoylbromide, dipropyl carbamoyl chloride dibutyl carbamoyl chloride, dihexylcarbamoyl chloride, dioctyl carbamoyl chloride, diphenyl carbamoylchloride, di (2-chlorophenyl) carbamoyl chloride, ethyl carbamoylchloride, amyl carbamoyl chloride, phenyl carbamoyl chloride, diB-naphthyl carbamoyl chloride.

Examples of suitable primary and secondary amines for reaction III (e)are methyl amine, ethyl amine, propyl amine, butyl amine, isopropylamine, sec. butyl amine, amyl amine, hexyl amine, cyclohexyl amine,octyl amine, isooctyl amine, dodecyl amine, aniline, otoluidine,p-toluidine, p-chloroaniline, m-choroaniline,

9 a-naphthyl amine, B-naphthyl amine, a-methyl-B- naphthyl amine,2-methyl-4-chloroaniline, piperidine, morpholine, 2-methyl piperidine,pyrrolidine, dimethyl amine, diethyl amine, allyl amine, dipropyl amine,di'

(isobropyl) amine, dibutyl amine, dihexyl amine di cyclohexyl amine,dioctyl amine, di lauryl amine ethyl propyl amine, N-methyl aniline,N-ethyl aniline, N- butyl aniline, diphenyl amine, o-chlor-l I-methylaniline, 2,4,6-trichloroaniline, 2,4,6-tribromo aniline.

Examples of carbamates and thiocarbamates within formula (4) are1,2,2-trichlor0ethyl dithioethyl N- methyl carbamate,2,2,2-trichloroethyl dithioethyLN- methyl carbamate,l,2,2,2-tetrachloroethyl dithioethyl N-methyl carbamate,1,2-dichloroethyl dithioethyl N- methyl carbamate, 1,2,2-tribromoethyldithioethyl-N- methyl carbamate, 2,2-dichlorovinyl dithioethyl-N- methylcarbamate, 1,2-dichlorovinyl dithioethyl-N- methyl carbamate,2,2-dibromovinyl dithioethyl-N- methyl carbamate, 1,2,2-trichloroethyldithi0ethyl-N- ethyl carbamate, 2,2,2-trichloroethyl dithioethyl-N-ethyl carbamate, 2,2-dichlorovinyl dithioethyl-N-ethyl carbamate,1,2,2-trichloroethyl dithioethyl-N-propyl carbamate,2,2,2-trichloroethyl dithioethyl-N-propyl carbamate, 2,2-dichlorovinyldithioethyl N-propyl carbamate, 2,2,2-trichloroethyldithioethyl-N-isopropy] carbamate, 1,2,2-trichloroethyldithioethyl-N-ethyl carbamate, 2,2,2-trichloroethyl dithioethyl-N-ethylcarbamate, 2,2-dichlorovinyl dithioethyl-N-ethyl carbamate,1,2,2-trichloroethyl dithioethyl-N-propyl carbamate, 2,2,-dichlorovinyldithioethyl N-propyl carbamate, 2,2,2-trichloroethyldithioethyl-N-isopropyl carbamate, 1,2,2-trichloroethyldithioethyl-N-butyl carbamate, 2,2,2-trichloroethyl dithioethyl-N-butylcarbamate, 2,2-clichlorovinyl dithioethyl-N-butyl carbamate,2,2-dichlorovinyl dithioethyl-N-sec butyl carbamate,1,2,2-trichloroethyl dithioethyl-N-amyl carbamate, 2,2-dichlorovinyldithioethyl-N-amyl carbamate, 2,2,2- trichloroethyl-dithioethyl-N-hexylcarbamate, 2,2- dichlorovinyl dithioethyl-N-hexyl carbamate, l,2,2-trichloroethyl dithioethyl-N-cyclohexyl carbamate, 2,2dichl0r0vinyldithioethyl-N-cyclohexyl carbamate, 2,2,2-trichloroethyldithioethyl-N-octyl carbamate, 2,2-dichlorovinyl dithioethyl-N-isooctylcarbamate, 1,2,2-trichloroethyl dithioethyl-N-dodecyl carbamate,2,2-dichlorovinyl dithioethyl-N-dodecyl carbamate, 1,2,2-trichloroethyldithioethyl-N-2'-chloroethyl carbamate, 1,2,2-trichloroethyldithioethyl-N-phenyl carbamate, 2,2,2-trichloroethyldithioethyl-N-phenyl carbamate, 2,2-dichlorovinyl dithioethyl-N-phenylcarbamate, 1,2,2-trichl0roethyl dithioethyl-N-p-tolyl carbamate,2,2,2-trichloroethyl dithioethyl-N-m-tolyl carbamate, 2,2-dichlorovinyldithioethyl-N-o-tolyl carbamate, 1,2,2-trichloroethyldithioethyl-N-p-ethylphenyl carbamate, 2,2-dichlorovinyldithioethyl-N-pbutylphenyl carbamate, 2,2,2-trichloroethyldithioethyl-N-p-chlorophenyl carbamate, 1,2,2-

trichloroethyl dithioethyl-N, 2',4,6'-trichlorophenyldithioethyl-piperidyl carbamate, 2,2-dichlorovinyl dithioethyl piperidylcarbamate, 1,2,2-trichloroethyl dithioethyl pyrrolidyl carbamate,2,2-dichlorovinyl dithioethyl pyrrolidyl carbamate, l,2,2-trichloroethyldithioethyl-N, N-dimethyl carbamate, 2,2,2-trichloroethyl dithioethyl-N,N-dimethyl carbamate, 2,2- dichlorovinyl dithioethyl-N, N-dimethylcarbamate, 1,2,2-trichloroethyl dithioethyl-N, N-diethyl carbamate,2,2,2-trichloroethyl dithioethyl-N, N-diethyl carbamate,2,2-dichlorovinyl dithioethyl-N, N-diethyl carbamate, 2,2-dibrom0vinyldithioethyl-N, N-diethyl carbamate, 1,2-dichlorovinyl dithioethyl-N,N-diethyl carbamate, l,2,2,2-tetrachloroethyl dithioethyl-N, N- diethylcarbamate, l,2-dichloroethyl dithioethyl-N, N- diethyl carbamate,1,2,2-trichloroethyl dithioethyl-N- ethyl-N-propyl carbamate,2,2-dichlorovinyl dithioethyl-N-ethyl-N-butyl carbamate, 1 ,2,2-trichloroethyl dithioethyl-N, N-dipropyl carbamate, 2,2,2-trichloroethyldithioethyl-N, N-dipropyl carbamate, 2,2-dichlorovinyl dithioethyl-N,N-dipropyl carbamate, 1,2,2-trichloroethyl dithioethyl-N, N- diisopropylcarbamate, 2,2-dichlorovinyl dithioethyl- N, N-diisopropyl carbmate,1,2,2-trichloroethyl dithioethyl-N, N-dibutyl carbamate,2,2,2-trichloroethyl dithioethyl-N, N-dibutyl carbamate,2,2-dichlorovinyl dithioethyl-N, N-dibutyl carbamate, 2 ,2 ,2-trichloroethyl dithioethyl-N, N-di sec. amyl carbamate,2,2-dichlorovinyl dithioethyl-N, N-diamyl carbamate,1,2,2-trichloroethyl dithioethyl-N, N-dihexyl carbamate,2,2-dichlorovinyl dithioethyl-N, N-dihexyl carbamate,2,2,2-trichloroethyl dithioethyl-N, N- dicyclohexyl carbamate,2,2-dichlorovinyl dithioethyl- N, N-dicyclohexyl' carbamate,1,2,2-trichloroethyl dithioethyl-N, N-diheptyl carbamate,2,2-dichlor0vinyl dithioethyl-N, N-dioctyl carbamate, 2,2,2-trichloroethyl dithioethyl-N, N-dilauryl carbamate, 2,2-dichlorovinyldithioethyl-N, N-dilauryl carbamate, 1,2,2-trichloroethyl dithioethyl-N,N-di3'-chloropropyl carbamate, 1,2,2-trichl0roethyl dithioethyl-N,-phenyl N-methyl carbamate, 2,2,2-trichloroethyl dithioethyl- N-phenylN-ethyl carbamate, 1,2,2-trichloroethyl dithioethyl-N, N-diphenylCarbamate, 2,2-dichlorovinyl dithioethyl-N, N-diphenyl carbamate, 2,2-dichlorovinyl dithioethyl-N, -phenyl N-methyl carbamate,l,2,2-trichloroethyl dithioethyl-N-m-tolyl N- methyl carbamate,2,2,2-trichloroethyl dithioethyl-N- o-tolyl N-ethyl carbamate,2,2-dichlor0vinyl dithioethyl-N-p-tolyl N-methyl carbamate,l,2,2-trichloroethyl dithioethyl-N-p-butylphenyl N-methyl carbamate,2,2-

dichlorobinyl dithioethyl-N-t-butyl-phenyl N-methyl carbamate,1,2,2-trichloroethyl ditiidethyl-N-ochlorophenyl N-butyl carbamate,2,2-dichlorovinyl dithioethyl-N 2', 4, 6'-trichlorophenyl N-methylcarbamate, 1,2,2-trichloroethyl dithioethyl-N-B-naphthyl N-methylcarbamate, 2,2-dichlorovinyl dithioethyl-N- a-naphthyl N-methylcarbamate, l,l,l-trichloro-3,4- dithiaheptane-6,7-di (N-methylcarbamate), 1,1,1- trichloro-3,4-di-thiaheptane-6,7-di (N,N-dimethylcarbamate), 1,1,l-trichloro 3,4-dithiaheptane-6,7di (N- ethylcarbamate), l,1,l-trichloro-3,4-dithiaheptane- 6,7-di (N, N-diethylcarbamate), l,l,2-trichloro-3,4- dithiaheptane-6,7-di (N, N-diethylcarbamate), 1,1,2- trichloro-3,4-dithiaheptane-6,7-di(N-ethylcarbamate), l,l-dichloro-3,4-dithiaheptene(-l )6,7-di (N- methylcarbamate), 1,l-dichloro-3,4-dithiaheptene(- l), 6,7-di (N,N-dime thylcarbamate), l,l-dichlor03,4- dithiaheptene(-l), 6,7-di (N-ethylcarbamate), 1,1-

dichloro-3,4-dithiaheptene-l ,6,7-di (N,N-diethyl carbamate), l l,2-trichloro-3,4-dithiaheptane-6,7-di (N- propyl carbamate),1,l-dichloro-3,4-dithiaheptane(- 1)6,7-di (N, N-dipropyl carbamate),l,l,l-trichloro- 3,4-dithiaheptane-6,7-di(N-butyl carbamate), 1 ,l,2-trichlor-3,4-dithiaheptane -6,7-di (N, N-dibutyl carbamate),l,l-dichloro-3, 4-dithiaheptene(-l )6,7-di (N- butyl carbamate),l,l-dichloro-3,4-dithiaheptene(- 1)6,7-di (N, N-dibutyl carbamate), 1,1,l-trichloro-3,4- dithiaheptane-6,7-di (N-phenyl carbamate), 1,1,2-trichloro-3,4-dithiaheptane-6,7-di(N, N-diphenyl carbamate),l,l-dichloro-3,4-dithiaheptene(-l )6,7-di (N- phenyl carbamate),1,l-dichloro3,4-dithiaheptene(- l)6,7-di (N, N-diphenyl carbamate),l,l,l-trichloro- 3 ,4-dithiaheptane-6,7-di( N-B-naphthyl carbamate l, l-dichloro-3,4-dithiaheptene(-l )6,7-di (N,N-di-anaphthyl carbamate l, l,2-trichloro-3,4- dithiaheptane-6,7-di (N, N-di-p-chlorophenylcarbamate), l,l -dichloro-3,4-dithiaheptene(-l )6,7-di (N-ochlorophenylcarbamate), 1,2,2-trichloroethyl dithioethyl N-methyl thiocarbamate,2,2-dichlorovinyl eithioethyl-N-methyl thiocarbamate, 2,2-trichloroethyldithioethyl-N-ethyl thiocarbamate, 1,2,2-trichloroethyl dithioethyl-N,N-diethyl thiocarbamate, 2,2- dichlorovinyl dithioethyl-N-ethylcarbamate, 2,2- dichlorovinyl dithioethyl-N, N-diethyl thiocarbamate,1,2,2-trichloroethyl dithioethyl-N, N-diisopropyl thiocarbamate,2,2,2-trichloroethyl dithioethyl-N-butyl thiocarbamate,1,2,2-trichloroethyl dithioethyl-N, N- dibutyl thiocarbamate,2,2-dichlorovinyl dithioethyl-N- butyl thiocarbamate, 2,2-dich1orovinyldithioethyl-N, N-dibutyl thiocarbamate, l ,2,2-trichloroethyldithioethyl-N-phenyl thiocarbamate, 2,2,2- trichloroethyl dithioethyl-N,N-diphenyl thiocarbamate, 2,2-dichlorovinyl dithioethyl-N-phenylthiocarbamate, 2,2-dichlorovinyl dithioethyl-N, N-diphenylthiocarbamate, 1,2,2-trichloroethyl dithioethyl N-ptolyl thiocarbamate,2,2,2-trichloroethyl-dithioethyl N,N-di-p-tolyl thiocarbamate,2,2-dichlorovinyl dithioethyl-N, M-di-p-tolyl thiocarbamate,l,l,2-trichloro- 3,4-dithiaheptane-6,7-di (nmethyl thiocarbamate), l,-l, l -trichloro-3,4-dithiaheptane-6,7-di (N, N-dibutyl thiocarbamate),l,l-dichloro3,4-dithiaheptene(-1 )6,7- di (ethyl thiocarbamate), l, l,l-trichloro-3,4- dithiaheptane-6,7-di (N-phenyl thiocarbamate), 1,1-dichloro-3,4-dithiaheptene(-l)6,7-di (N, N-diphenyl thiocarbamate), l,1-dichloro-3,4dithiaheptene(-l )6,7- di (N-p-tolyl thiocarbamate).

The compounds of formula (5 are made by reacting the appropriate alcoholof formula (1) with phosgene or thiophosgene.

Examples of compounds within formula (5) are: 1,2,2-trichloroethyldithioethyl chloroformate, 2,2,2-

tfichloroethyl kfithTopropyl- T, 3 -di (chloroformate),2,2,2-trichloroethyl dithiopropyl-2',3'-di (chloroformate),2,2-dichlorovinyl dithiopropyl-2',3'-di (chloroformate),1,2,2-trichloroethyl dithioethyl-thiono chloroformate,2,2,2-trichloroethyl dithioethyl-thiono chloroformate, 2,2-dichlorovinyldithioethyl-thiono chloroformate, l,2,2-trichloroethyl dithiopropyl-2 ,3'di (thiono chloroformate), 2,2,2-trichloroethyl dithiopropyl-2', 3-di(thiono chloroformate), 2,2- dichlorovinyl dithiopropyl-Z', 3'-di(thiono chloroformate).

The compounds of formula (6) are prepared by reacting a dicarboxylicacid chloride or bromide with the appropriate monohydric alcohol withinformula (1). If two moles of the alcohol are employed per mole of thedicarboxylic acid halide then a his ester is formed; with equimolaramounts of alcohol and dicarboxylic acid halide there is formed a halfester. The acid halide group in the latter case is then hydrolyzed tofree acid with aqueous acid, e.g. hydrochloric acid or with a base suchas sodium hydroxide or potassium hydroxide. If excess base is employedthere is obtained the half salt, e.g. the sodium mono salt or potassiummono salt.

Examples of suitable dicarboxylic acid halides are oxalyl chloride,oxalyl bromide, malonyl chloride, succinyl chloride, phthalyl chloride,tetrachlorophthalyl chloride, 4-chlorophthalyl chloride, fumarylchloride, maleyl chloride, terephthalyl chloride, isophthalyl chloride.

Examples of compounds within formula (6) are bis-(2,2,2-trichloroethyldithioethyl) oxalate, bis-(2,2- dichlorovinyl dithioethyl) oxalate,bis-( 1 ,2,2,2-tetrachloroethyl dithioethyl oxalate,bis-(1,2-dichloroethyl dithioethyl) oxalate, bis-( l,2,2-tribromoethyldithioethyl) oxalate, bis-(1,2-dibromovinyl dithioethyl) oxalate,bis-(1,2,2-trichloroethyl dithioethyl) malonate,bis-(2,2,2-trichloroethyl dithioethyl malonate, bis-(2 ,2-

dichlorovinyl dithioethyl) malonate, bis-( 1 ,2,2- trichloroethyldithioethyl) succinate, bis-(2,2,2- trichloroethyl dithioethyl)succinate bis-( 2 ,2- dichlorovinyl dithioethyl) succinate, bis-( 1,2,2- trichloroethyl dithioethyl) maleate, bis-( 2,2 ,2- trichloroethyldithioethyl) maleate bis-( 2 ,2- dichlorovinyl dithioethyl) maleate,bis-( 1,2 ,2- trichloroethyl dithioethyl) fumarate bis-( 2 ,2 ,2-trichloroethyl dithioethyl) fumarate, bis-( 2 ,2- dichlorovinyldithioethyl) fumarate, bis-( 1,2,2- trichloroethyl dithioethyl)phthalate bis-( 2 ,2 ,2- trichloroethyl dithioethyl) phthalate, bis-( 1,2,2- trichloroethyl dithioethyl) terophthalate, bis-(2,2,2-trichloroethyl dithioethyl) terephthalate, bis-(2,2- dichlorovinyldithioethyl) terephthalate, bis-( 1 ,2,2- trichloroethyl dithioethyl)isophthalate, bis-(2,2- dichlorovinyl dithioethyl) isophthalate,bis-(2,2,2- trichloroethyl dithioethyl) tetrachlorophthalate, bis-(2,2-dichlorovinyl dithioethyl) tetrachlorophthalate, bis-( 1,2,2-trichloroethy1 dithioethyl) 4- chlorophthalate,mono-1,2,2-trich1oroethyl dithioethyl oxalate, mono-2,2-dichloroethyldithioethyl oxalate) mono-2,2,2-trichloroethyl dithioethyl phthalate.

Unless otherwise indicated all parts and percentages are by weight.

METHODS OF PREPARATION I. Alcohols (A) The saturated halo-disulfidealcohols of formula (I) are prepared generally by the dropwise additionof the chosen saturated sulfenyl halide in equimolar amounts to theappropriate mercapto-alcohol in an inert solvent. Such solvents includehalohydrocarbons such as chloroform, carbon tetrachloride, andtetrachloroethane and hydrocarbons such as benzene, toluene, xylene,hexane, cyclohexane, petroleum ether, and aromatic naphtha. The reactiontemperature in the examples below was 25-30C. which temperature wasmaintained by cooling with an ice-water bath; completion of the reactionwas determined by a negative reaction to KI-starch test paper. Isolationwas accomplished by washing the reaction mixture with water drying andvacuum stripping.

(B) The unsaturated halo disulfide alcohols within formula (1) wereprepared by dehydrohalogenation of the saturated halo-disulfide alcoholswith equivalent amounts of sodium ethoxide. In place of sodium ethoxidethere can be used potassium ethoxide and other alcoholates having up tothree carbon atoms, e.g. sodium methylate, sodium propylate, sodiumisopropylate, potassium propylate. The reaction temperature wasmaintained at 25-30C. through cooling with an ice-water bath. Dilutionwith water furnished the products as bottom oils.

II. Carbonates, Thiol Carbonates, Dithiocarbonates The poly halodisulfide carbonates, thiol carbonates and dithiocarbonates withinformulae (2) and (3) were prepared by three routes:

(A) By the reaction of the polyhalo disulfide alcohol of formula (1)with the chosen chloroformate, e.g. alkyl or aryl chloroformate. Thealcohol and chosen chloroformate were mixed together and heated at atemperature between 85 and l20C. (This temperature range can be variedif desired.) Reaction times normally were in the order of several hoursand the reaction was completed on the disappearance of the hydroxylabsorption in the infrared spectrum analysis.

(B) By the reaction of a polyhalo disulfide chloroformate of formula anda chosen alcohol (e.g. alkyl or aryl alcohol) or mercaptan under thesame general condition as described in ll(A). in this reaction it wasalso observed that there was a shift to a lower frequency by the C=O inthe infrared spectrum of the formed carbonate. In some instances atertiary base was used toforce the reaction. Such tertiary bases includetrialkyl amines such as trimethyl amine, triethyl amine, tripropylamine, and triamyl amine, pyridine, dimethyl aniline, diethyl aniline(and other tertiary aromatic amines) quinoline, a-picoline, B-picoline,lutidine.

(C) By the reaction of a chosen polyhalo sulfenyl chloride with anappropriate mercapto carbonate under the same conditions as described inl(A).

Ill. Carbamates The polyhalo disulfide carbamates of formula (4) wereprepared by three routes:

(A) By reaction of the chosen polyhalo disulfide alcohol of formula lwith an appropriate organic isocyanate (or isothiocyanate), e.g. analkyl or aryl isocyanate. The reagents are mixed and heated to 95 to110C. (This temperature can be varied somewhat if desired). The progressof the reaction was observed by periodic infrared scans. It was completeupon the disappearance of both the OH and N-C--O absorption.

('8) By the reaction of a polyhalo disulfide alcohol with an appropriatecarbamoyl chloride. The two reactants were mixed and warmed at 80 to100C. until the reaction was complete.

(C) By the reaction of a polyhalo disulfide chloroformate of formula (5)with a primary or secondary amine. Two equivalents of the amine wereadded dropwise at 25 30C. to one equivalent of the chloroformate tofurnish the product in a quantitative yield. IV. Esters The esters offormula (2) (other than carbonates, thiolcarbonates anddithiocarbonates) and formula (6) were formed by reacting the polyhalodisulfide alcohol of formula (1) with an appropriate acyl chloride, e.g.an alkyl chloride or aryl chloride in an inert solvent at 30 to C.Suitable solvents include hydrocarbons and halohydrocarbons such asthose set forth in Method I(A). The alcohol and acyl chloride are usedin equimolar amounts except that when employing the acyl chlorides ofdibasic acids there were used two moles of alcohol per mole of acylhalide to form the diester. V. The polyhalo disulfide chloroformates offormula (5) were prepared by two routes:

(A) by allowing a mixture of the chosen halo disulfide alcohol offormula l and either phosgene or thiophosgene to stand at roomtemperature and atmospheric pressure, in an inert solvent (such as thoseset forth in Method I(A)), for several days until an infrared analysisshows the disappearance of the OH absorption and appearance of the OO--CI absorption.

(B) By heating the same mixture as in V(A) in a sealed tube at -90C. forseveral hours. The degree of completeness of the reaction was determinedby infrared analysis.

EXAMPLE 1 Compound 5598 l,2,2-trichloroethyl-B-hydroxyethyl disulfideOne hundred grams of 1,2,2-trichloroethyl sulfenyl chloride (0.5 M)reacted at 2530C. with 39 grams of 2-mercaptoethanol in 50 ml. of CI-IClas described in Method I-A furnished 1,2,2-trichloroethyl-B-hydroxyethyldisulfide in a 92 percent yield as a faintly yellow oil having n 1.5783.

EXAMPLE 2 EXAMPLE 3 Compound 5464l,2,2-trichl0roethyl-2',3-dihydroxypropyl disulfide When one hundredgrams l,2,2-trichloroethyl sulfenyl chloride (0.5 M) were reacted at2530C. with 54 grams monothioglycerol (0.5M) in 50 ml. of CHCl by MethodLA, 1 ,2,2-trichloroethyl-2 3-dihydroxypropyl disulfide was obtained inan 86 percent yield as an orange colored oil, n 1.5804.

EXAMPLE 4 Compound 6465 2,2,2-trichloroethyl-2',3'-dihydroxypropyldisulfide The reaction of 185 grams 2,2,2-trichloroethyl sulfenylchloride (0.925 M) at 20C. with l00 grams monothioglycerol (0.925 M) ingrams of CHCl produced 2,2,2-trichloro-2, 2'-dihydroxypropyl disulfidein a quantitative yield as a thick colorless oil that solidifies. mp.46-47C.

EXAMPLE Compound 6467 2,2-dichlorovinyl-B-hydroxy-ethyl disulfide When48.3 grams 5607 (Ex. 2, 0.2 M) were dehydrochlorinated at 20-25C. asdescribed in Method LB with one equivalent of sodium ethoxide in 150 ml.of 1 ethanol, 2,2-dichlorovinyl-B-hydroxyethyl disulfide was obtained inan 86 percent yield as a reddish oil, n 1.6145.

EXAMPLE 6 Compound 6466 2,2-dichlorovinyl-2',3'-dihydroxypropyldisulfide Reaction at 20-25C. of one equivalent sodium ethoxide in 150grams of ethanol with 54.3 grams 6465 (Ex. 4, 0.2 M) by Method l-Bfurnished 2,2- dichlorovinyl-2,3'-dihydroxypropyl disulfide in a 90percent yield as a reddish oil n 1.5930.

EXAMPLE 7 Compound 5420 1,2,2-trich1oroethyldithioethylethyl carbonateWhen 20 grams of 1,2,2-trich1oroethy1 sulfenyl chloride (0.1 M) werereacted at 30-35C. with 15.02 grams ethyl-2-mercaptoethyl-carbonate(0.1M) as described in Method ILC, using 100 ml. of CHCl as a solventl,2,2-trichloroethyldithioethyl-ethyl carbonate 5420 was obtained in a97 percent yield as a faintly yellow oil, b l31-2 C., n 1.5346.

EXAMPLE 8 Compound 5422 2,2,2-trichloroethyldithioethylethyl carbonateTwenty grams of 2,2,2-trich1oroethyl sulfenyl chloride (0.1 M) whenreacted at 30-35C. with 15.02 grams ethy1-2-mercaptoethyl-carbonate (0.1M) as in Method II-C using 100 ml. of CHCl as a solvent fur nished2,2,2-trichloroethyldithioethyl-ethyl carbonate in a 96 percent yield asa peach colored oil, n 1.5263.

EXAMPLE 9 Compound 6463 -1 ,1 ,2-trichloro-3,4-dithia-heptane- 6,7-di(ethyl carbonate) Reaction of 27.15 grams 5464 (0.1 M, Ex. 3) with 25grams ethyl chloroformate (0.23 M, 15 percent excess) as described inMethod ll-A furnished 1,1,2-trichloro- 3,4-dithiaheptane-6,7-di(ethylcarbonate) in a 94 percent yield as a yellow oil, n 1.5480.

EXAMPLE 10 EXAMPLE 1 1 Compound 6478 2,2,2-trichloroethyldithioethyl-S-ethyl thiol carbonate Reaction of 7 grams2,2,2-trichloroethyldithioethylchloroformate (Ex. 34) in 25 ml. of CHCl(0.023 M) with 2.8 grams ethyl mercaptan (0.046 M, percent excess) and2.35 grams Et N (0.023 M) at 25C. in Method lI-B furnished2,2,2-trichloroethyldithioethyl- 0 S-ethyl thio carbonate in a 92percent yield as a dark oil, n 1.5581.

EXAMPLE 12 Compound 6464 -1 ,1 ,2-trichloro-3,4-dithiaheptane-6,7-di(ethylthiol carbonate) When 27.15 grams of 5464 (0.1 M, Ex. 3)were reacted with 30 grams ethyl chlorothiol formate (0.24 M, 20 percentexcess) as described in Method II-A, 1,1 ,2-trichloro-3,4-dithiaheptane-6,7-di(ethylthiol carbonate) was obtained inan 88 percent yield as a dark yellow oil, n 1.5565.

EXAMPLE 13 Compound 6759 1,2,2-trichloroethyldithioethyl-S- ethyldithiocarbonate Addition of 2.0 grams of Et N (0.02 M) to a mixture of6.4 grams of 1,2,2-trichloroethyldithioethyl-thiono chloroformate (Ex.38) (0.02 M) and 1.2 grams of ethyl mercaptan (0.02 M) n 25 ml of 3:1benzenezpet. ether at 35C. in Method "-8 resulted in 1,2,2-trichloroethyldithioethyl-S-ethyl dithiocarbonate in a quantitativeyield as an orange oil, n 1.5840.

EXAMPLE 14 Compound 5606 1,2,2-trichloroethyl dithioethylphenylcarbonate 24.15 grams of 5598 (0.1 M Ex. 1) when reacted at 65C (reflux)in ll-A with 15.65 grams phenyl chloroformate (0.1M) in 50 ml. of Cl-lClfurnished 1,2,2- trichloroethyldithioethyl-phenyl carbonate in an 81percent yield as a yellow oil, n 1.5695.

EXAMPLE 15 Compound 6555 2,2,2-trichloroethyldithioethylphenyl carbonateReaction of 24.15 grams 5607 (0.1 M, Ex. 2) with 17.65 grams phenylchloroformate (0.113 M, 9 percent excess) at 1 14-120C. as described inll-A resulted in a quantitative yield of2,2,2-trichloroethyldithioethylphenyl carbonate as a dark yellow oil, n1.5632.

EXAMPLE 16 Compound 6554 1,2,2-trichloroethyldithioethyl-S- phenyl thiolcarbonate When 24.15 grams of 5598 (0.1 M, Ex. 1) were reacted with19.25 grams of phenyl chlorothiol formate (0.1 12 M, 9 percent excess)at 1 15120C in ll-A, 1,2- ,2-trichloroethyldiethioethyl-S-phenyl thiolcarbonate was obrained in a 97 percent yield as a dark oil, n 1.5967.

EXAMPLE 17 Compound 6556 2,2,2-trichloroethyldithioethyl-S- phenyl thiolcarbonate 24.15 grams of 5607 (0.1 M, Ex. 2) were reacted at 1l5-120C.as in II-A with 19.25 grams of phenyl chlorothiolformate (0.1 12 M, 9percent excess), to obtain 2,2,2-trichloroethyldithioethyl-S-phenylthiol carbonate in a quantitative yield as a dark yellow oil, n 1.5932.

EXAMPLE 18 Compound 6808 2,2-dichlorovinyl dithioethylethyl carbonateReaction of 5.35 grams of 2,2-dichlorovinyl dithioethyl chloroformate(Ex. 35) (0.02 M) with absolute EtOH (50 ml.) at 80C as described inMethod ll-B resulted in 2,2-dichlorovinyldithioethyl-ethyl carbonate ina quantitative yield as a dark oil, n 1.5740.

EXAMPLE 19 Compound 6553 2,2-dichlorovinyldithioethyl phenyl carbonateWhen 20.5 grams of 6467 (0.1 M, Ex. were reacted with 17.65 grams ofphenyl chloroformate (0.1 13 M, 9 percent excess) at l 10-1 C. in ll-Athere was obtained 2,2-dichlorovinyldithioethyl phenyl carbonate in aquantitative yield as a dark oil, n 1.5785.

EXAMPLE EXAMPLE 21 Compound 6479bis-(2,2,2-trichloroethyldithioethyl)-carbonate When 7 grams of2,2,2-trichloroethyldithioethyl chloroformate (0.023 M) were reactedwith 5.55 grams of 5607 (0.023 M, Ex. 2) at ll5-125C. in ll-A, bis-(2,2,2-trichloroethyldithioethyl) carbonate was obtained in a 95 percentyield as a dark oil, 11,, 1.5839.

EXAMPLE 22 Compound 6757 (l,2,2-trichloroethyldithioethyl)-(2,2-dichlorovinyldithioethyl) carbonate Reaction of 3 grams of1,2,Z-trichloroethyldithioethyl chloroformate (Ex. 33) (0.01 M) with 2grams of 6467 (0.01 M, Ex. 5) in 50 ml. of benzene in the presence of 1gram Et N (0.01 M) in 11-3 resulted in a 90 percent yield ofl,2,2-trichloroethyldithioethyl)-(2,2- dichlorovinyldithioethyl)carbonate as a brown oil.

EXAMPLE 23 Compound 6760 -0-[B-( 1,2,2-trichloroethyldithio)ethyl]-S-[0-ethyl-thiocarboxyl]- dithio carbonateThe reaction of 6.4 grams of 1,2,2-trichloroethyldithioethyl thionochloroformate (0.02 M) with 7.2 grams potassium ethyl xanthate (0.045 M,125 percent excess) in 100 ml. of tetrahydrofuran containing 3% water at25C. medium furnishes, after washing with water, drying and vacuumstripping gave 0-[B-(l,2,2-trichloroethyldithio)ethyl]-S-[O-ethyl-thiocarboxylldithio carbonate asa dark oil n 1.6111.

EXAMPLE 24 Compound 5604 1,2,2-trichloroethy1dithioethyl-N, N-diethylcarbamate When 24.15 grams of 5598 (0.1 M, Ex. 1) were reacted in 50 ml.of CHCl with 13.55 grams diethyl carbamoylchloride (0.1 M) as describedin Ill-B, 1,2,2- trichloroethyldithioethyl-N, N-diethyl carbamate wasobtained in an percent yield as a faintly yellow oil,

EXAMPLE 25 Compound 6810 2,2-dichlorovinyldithioethylN, N- diethylcarbamate Reaction of 5.35 grams of 2,2dichlorovinyldithioethylchloroformate (0.02 M) in 50 ml. of benzene with 2.92 grams of diethylamine (0.04 M) at 2530C. in Ill-C resulted in2,2-dichlorovinyldithioethyl-N, N- diethyl carbamate ina quantitativeyield as a dark 01].

EXAMPLE 26 Compound 6451 1,2,2-trichloroethyldithioethyl-N- phenylcarbamate 24.15 grams of 5598 (0.1 M, Ex. 1) when reacted with 12 gramsof phenyl isocyanate (0.1 M) at -95C. as described in III-A furnished1,2,2- trichloroethyldithioethyl-N-phenyl carbamate in an 89 percentyield as a thick oil.

EXAMPLE 27 Compound 6452 2,2,2-trichloroethyldithioethyl-N- phenylcarbamate When 24.15 grams of 5607 (0.1 M, Ex. 2) were reacted with 12grams of phenyl isocyanate (0.1 M) at 9095C. as in "LA2,2,2-trichloroethyldithioethyl-N- phenyl carbamate was obtained in a 70percent yield asa heavy oil.

EXAMPLE 28 Compound 6795 l,2,2-trichloroethyldithio-ethyl acetate 1Reaction of 24.15 grams of 5598 (0.1 M, Ex. 1) with 7.85 grams of acetylchloride (0.1M) in 50 ml. of benzene at 8085C. as described in IVresulted in 1,2,2- trichloroethyldithioethyl acetate in a 97 percentyield as a faintly yellow oil, n 1.5460.

EXAMPLE 29 Compound 6796 2,2,2-trichloroethyldithioethyl acetate When24.15 grams of 5607 (0.1 M, Ex. 2) were reacted with 7.85 grams ofacetyl chloride (0.1 M) in 50 ml. of benzene at 8085C. in Method 1V,2,2,2- trichloroethyldithioethyl acetate was obtained in a percent yieldas a faintly yellow oil, n 1.5440.

EXAMPLE 30 Compound 6797 2,2-dichlorovinyldithioethyl acetate 6.15 gramsof 6467 (0.03 M, Ex. 5) when reacted with 2.36 grams of acetyl chloride(0.03 M) in 25 ml. of benzene at 8085C. in 1V, furnished2,2-dichlorovinyldithioethyl acetate in a 95 percent yield as a darkoil, n 1.5808.

EXAMPLE 31 Compound 675 8 l,2,2-trichloroethyl-2,3- diacetoxypropyldisulfide Reaction of 27.15 grams of 5464 (0.1 M, Ex. 3) with 17.7 gramsof acetyl chloride (0.226 M, 12% excess) in 100 ml. of benzene at 40C.as described in 1V resulted in 1,2,2-trichloroethyl-2, 3-diacetoxypropyldisulfide in a 90 percent yield as a faintly yellow oil, n 1.5280.

EXAMPLE 32 Compound 6761 bis-(2,2,2-trichloroethyldithioethyl )oxalateWhen 24.15 grams of 5607 (0.1M, Ex. 2) were reacted with 6.35 grams ofoxalyl chloride (0.05 M) in 100 ml. of benzene at 35C. as in 1V, bis(2,2,2- trichloroethyldithioethyl oxalate was obtained in a 98 percentyield as a thick yellowish oil.

EXAMPLE 33 1,2 ,2-trichloroethyldithioethyl chloroformate Allowing amixture of 24.2 grams of 5598 (0.1 M, Ex. 1) and 12 grams of phosgene(0.121M, 20 percent excess) to stand at room temperature in 125 ml. drybenzene for three days, resulted in 1,2,2-trichloroethyldithio-ethylchloroformate as a light yellow oil in a 92 percent yield, n 1.5530.

EXAMPLE 34 2,2,2-trichloroethyldithioethyl chloroformate Mixing 12.08grams of 5607 (0.05 M, Ex. 2) with 7.5 grams of phosgene (0.0757 M, 50percent excess) in 125 ml. of benzene under the same conditions as inEx. 33 resulted in 2,2,2-trichloroethyldithioethyl chloroformate in a 96percent yield as a light yellow oil.

EXAMPLE 35 2,2-dichlorovinyldithioethyl chloroformate Heating a mixtureof 15 grams of 6467 (0.073 M, Ex. 5) and 10 grams of phosgene (0.101 M,70 percent excess) in 100 ml. dry benzene in a sealed tube at 8085 C.and allowing'to stand at room temperature overnight furnished2,2-dichlorovinyldithioethyl chloroformate in a 95 percent yield asreddish oil, n 1.5915.

EXAMPLE 36 1 ,2,2-trichloroethyldithiopropyl-2 ,3 '-di-(chloroformate) Amixture of 27.2 grams of 5464 (0.1 M, Ex. 3) and 24 grams of phosgene(0.242 M, 20 percent excess) in 100 ml. benzene was allowed to stand atroom temperature for 3 days. At the end of this period the mixture wasvacuum stripped and a portion (10 grams) of the residue mixed with 10grams of phosgene (0.1 1 M) in 100 ml. benzene and heated in a sealedtube at 80-85 C. for 5 hours. This completed the reaction as evidencedby the infrared scan to give 1,2,2-trichloroethyldithiopropyl-Z ,3'-di-(chloroformate).

EXAMPLE 37 2,2,2-trichloroethyldithiopropyl-2,3-di- (chloroformate)Heating a mixture of 27.2 grams of 6465 (0.1 M, Ex. 4) and 24 grams ofphosgene (0.242 M, 21 percent excess) in 100 ml. benzene, then removingthe benzene and heating at 70C. and 0.05 mm. Hg. for 1 hour fur- 20nished 2,2,2-trichloroethyldithiopropyl-2 ,3 '-di- (chloroformate) in anpercent yield as a yellow oil, n 1.5780.

EXAMPLE 38 EXAMPLE 39 The procedure of Example 14 was repeated,replacing the phenyl chloroformate by 0.1 mole of butyl chloroformate toproduce 1,2,2-trichloroethyldithioethyl butyl carbonate.

EXAMPLE 40 The procedure of Example 8 was repeated, replacing theethyl-2mercaptoethyl-carbonate by 0.1 mole of methyl-Z-mercaptoethylcarbonate to produce 2,2,2- trichloroethyldithoethyl-methyl carbonate.

EXAMPLE 41 The procedure of Example 28 was repeated, replacing theacetyl chloride by 0.1 mole of benzoyl chloride to producel,2,2-trichloroethyldithioethyl benzoate.

EXAMPLE 42 The procedure of Example 30 was repeated, replacing theacetyl chloride by 0.03 mole of p-chlorobenzoyl chloride to produce2,2-dichlorovinyldithioethyl pchlorobenzoate.

EXAMPLE 43 The procedure of Example 29 was repeated, replacing theacetyl chloride by 0.1 mole of butyryl chloride to produce2,2,2-trichloroethyldithioethyl butyrate.

EXAMPLE 44 The procedure of example 28 was repeated, replacing theacetyl chloride by 0.1 mole of trichloroacetyl chloride to produce1,2,2-trichloroethy1dithioethyl trichloroacetate.

EXAMPLE 45 The procedure of example 25 was repeated, replacing thediethyl amine with 0.04 mole of dimethyl amine to produce2,2-dichlor0vinyldithioethyl-N-N-dimethyl carbamate.

EXAMPLE 46 The procedure of example 24 was repeated, replacing thediethyl amine with 0.04 mole of dibutyl amine to produce1,2,2-trichloroethyldithioethyl-N,N-dibuty1 carbamate.

EXAMPLE 47 The procedure of Example 25 was repeated, replacing thediethyl amine with 0.04 mole of mono propyl amine to produce2,Z-dichlorovinyldithioethyl-N- propyl carbamate.

EXAMPLE 48 The procedure of Example 26 was repeated, replacing thephenyl isocyanate by 0.1 mole of a-naphthyl isocyanate to produce1,2,2-trichloroethyldithioethyl- N-a-naphthyl carbamate.

EXAMPLE 49 The procedure of Example 25 was repeated, replacing thediethyl amineby 0.04 mole of N-methyl aniline to produce2,2-dichlorovinyldithioethyl-N-phenyl-N- methyl carbamate.

EXAMPLE 50 The procedure of Example 25 was repeated, replacing thediethyl amine with 0.04 mole of diphenyl amine to produce2,2dichlorovinyldithioethyl-N,N-diphenyl carbamate.

EXAMPLE 51 The procedure of Example 25 was repeated, replacing thechloroformate with 0.01 mole of 1,2,2-trichloroethyldithiopropyl-2,3'-di-(chloroformate) to produce 1 ,l,2-trichloro-3 ,4-dithiaheptane-6,7-di- (N,N-diethyl carbamate).

EXAMPLE 52 The procedure of Example 36 was repeated, replacing Compound5464 with 0.1 mole of Compound 6466 to produce2,2-dichlorovinyldithiopropyl-2,3'-di- (chloroformate).

EXAMPLE 53 The procedure of Example 25 was repeated, replacing thediethyl amine by 0.04 mole of morpholine to produce2,2-dichlorovinyldithioethyl morpholino carbamate.

EXAMPLE 54 The procedure of Example 25 was repeated, replacing thechloroformate by 0.02 mole of 2,2,2- trichloroethyldithioethylchloroformate and the diethyl amine by 0.04 mole of piperidine toproduce 2,2,2- trichloroethyldithioethyl-piperidyl carbamate.

EXAMPLE 55 The procedure of Example 32 was repeated, replacing theoxalychloride by 0.05 mole phthalyl chloride to producebis-(2,2,2-trichloroethy1dithioethyl) phthalate.

EXAMPLE 56 The procedure of Example 32 was repeated, replacing Compound5607 by 0.1 mole of Compound 6467 and replacing the oxalyl chloride by0.05 mole of succinyl chloride to producebis-(2,2-dichlorovinyldithioethyl) succinate.

EXAMPLE 57 The procedure of Example 32 was repeated, replacing theoxalyl chloride by maleyl chloride to produce bis-(2,2,2-trichloroethyldithioethyl) maleate.

EXAMPLE 58 Reaction of 24.15 grams (0.1 mole) of 1,2,2-trichloroethyl-B-hydroxyethyl disulfide (Compound 5598) with 11.3 gramsof chloroacetyl chloride (0.1

'mole) in 100 ml. of dry benzene at 85C. gave 1,2,2-

trichloroethyl dithioethyl chloroacetate (Compound 7108) in aquantitative yield as a dark yellow oil, n 1.5552.

EXAMPLE 59 Reaction of 12.0 grams (0.1 M) of Compound 5598 with 9.1grams (0.05 M) of trichloroacetyl chloride in 50 ml. of dry benzene at50C. gave a 91 percent yield of l,2,2-trichloroethyldithioethyltrichloroacetate (Compound 7279) as a dark oil, n 1.5550.

EXAMPLE 60 Reaction of 24.15 grams (0.1 M) of Compound 5598 with 14.06grams (0.1 M) of benzoyl chloride in 100 ml. of dry benzene at 85C.furnished 1,2,2- trichloroethyldithioethyl benzoate (Compound 7109) as adark yellow oil in a yield of 92 percent.

EXAMPLE 61 Reaction of 24.15 grams (0.1 M) of Compound 5598 with 16.7grams (0.1 M) of cinnamoyl chloride in 100 ml. of dry benzene at 85C.gave a quantitative yield of 1,2,2-trichloroethyldithioethyl cinnamate(Compound 71 10) as an orange-yellow oil.

EXAMPLE 62 Reaction of 12.0 grams (0.05 M) of Compound 5598 with 8.53grams of phenoxyacetyl chloride in 50 ml. of dry carbon tetrachloride atC. gave a 96 percent yield of l,2,2-trichloroethyldithioethylphenoxyacetate (Compound 7280) as a yellow oil.

EXAMPLE 63 12.0 grams (0.05 M) of 1,2,2-trichloroethyl-B- hydroxyethyldisulfide (Compound 5598) were reacted with 10.95 grams (0.05 M) of2-methy1 -4-chlorophenoxyacetyl chloride in 50ml. of dry carbontetrachloride at 80C. to give a 99 percent yield of 1,2,2-trichloroethyldithioethyl-2-methyl-4'- chlorophenoxyacetate as a yellowoil.

EXAMPLE 64 EXAMPLE 65 Reaction of 24.15 grams (0.1 M) of Compound 5607with 14.06 grams (0.1 M) of benzoyl chloride in 100 ml. of dry benzeneat C. gave a 97 percent yield of 2,2,Z-trichloroethyldithioethylbenzoate (Compound 7205) as a dark yellow oil, n 1.5760.

EXAMPLE 66 24.15 grams (0.1 M) of Compound 5607 were reacted with 16.7grams (0.1M) of cinnamoyl chloride in ml. of dry benzene at 85C. to givean 89 percent yield of 2,2,Z-trichloroethyldithioethyl cinnamate(Compound 7206) as a yellow oil, n 1.6020.

EXAMPLE 67 Reaction of 14.6 grams (0.0712 M) of 2,2

dichlorovinyl-B-hydroxyethyl disulfide (Compound 6467) with 8.05 grams(0.0712 M) of chloroacetyl chloride in 100 ml. of dry benzene at 85C.gave a 99 percent yield of 2,2-dichlorovinyldithioethyl chloroacetate(Compound 7201) as a dark oil, n 1.5685.

EXAMPLE 68 Reaction of 13.3 grams (0.065 M) of Compound 6467 with 9.15grams (0.065 M) of benzoyl chloride in 100 ml. of dry benzene at 85C.gave an 89 percent yield of 2,2-dichlorovinyldithioethyl benzoate(Compound 7202) as a dark oil, n 1.5915.

EXAMPLE 69 Reaction of 12.25 grams (0.0597 M) of Compound 6467 with 9.95grams (0.597 M) of cinnamoyl chloride in 100 ml. of dry benzene at 85C.gave a quantitative yield of 2,2-dichlorovinyldithioethyl cinnamate(Compound 7203) as a dark oil, D25 1.6240.

EXAMPLE 70 Reaction of 13.3 grams (0.065 M) of Compound 6467 with 4.72grams (0.0325 M) of fumaryl chloride in 100 ml. of dry benzene at 85C.gave a 99 percent yield of bis (2,2-dichlorovinyldithioethyl) fumarate(Compound 7224) as a thick yellow oil, n 1.5958.

The products of the present invention can be used alone or they can beapplied together with inert solids to form dusts, or can be suspended ina suitable liquid dilent, e.g., organic solvents or water.

There can also be added surface active agents or wetting agents and/orinert solids in the liquid formulations. In such case, the activeingredient can be from 0.01 to 95 percent by weight of the entirecomposition.

As organic solvents there can be employed hydrocarbons, e.g. benzene,toluene, xylene, kerosene, diesel fuel, fuel oil, and petroleum naphtha,ketones such as acetone, methyl ethyl ketone and cyclohexanone,chlorinated hydrocarbons such as carbon tetrachloride, chloroform,trichloroethylene, and perchloroethylene, esters such as ethyl acetate,amyl acetate and butyl acetate, ethers, e.g., ethylene glycol monomethylether and diethylene glycol monomethyl ether, alcohols, e.g., methanol,ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol,butyl carbitol acetate and glycerine. mixtures of water and organicsolvents, either as solutions or emulsions, can be employed.

The novel products can also be applied as aerosols, e.g., by dispersingthem in air by means of a compressed gas such as dichlorodifluoromethaneor trichlorofluoromethane and other Freons and Genetrons, for example.

The products of the present invention can also be applied with adjuvantsor carriers such as talc, pyrophyllite, synthetic fine silica,attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calciumcarbonate, bentonite, fullers earth, cottonseed hulls, wheat flour,soybean flour, pumice, tripoli, wood flour, walnut shell flour, redwoodflour and lignin.

As stated, it is frequently desirable to incorporate a surface activeagent in the compositions of the present invention. Such surface activeor wetting agents are advantageously employed in both the solid andliquid compositions. The surface active agent can be anionic, cationicor nonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts,alkylaryl sulfonate salts, alkylaryl polyether alcohols, fatty acidesters of polyhydric alcohols and the alkylene oxide addition productsof such esters, and addition products of long chain mercaptans andalkylene oxides. Typical examples of such surface active agents includethe sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in thealkyl group, alkylphenol ethylene oxide condensation products, e.g.,pisooctylphenol condensed with 10 ethylene oxide units, soaps, e.g.,sodium stearate and potassium oleate, sodium salt of propyl-naphthalenesulfonic acid, di (2- ethylhexyl) ester of sodium sulfosuccinic acid,sodium lauryl sulfate, sodium decane sulfonate, sodium salt of thesulfonated monoglyceride of coconut fatty acids, sorbitan sesquioleate,lauryl trimethyl ammonium chloride, octadecyl trimethyl ammoniumchloride, polyethylene glycol lauryl ether, polyethylene glycol estersof fatty acids and rosin acids, e.g., Ethofat 7 and 13, sodiumN-methyl-N-oleyl taurate, Turkey Red Oil, sodium dibutyl naphthalenesulfonate, sodium lignin sulfonate, polyethylene glycol stearate, sodiumdodecylbenzene sulfonate, tertiary dodecyl polyethylene glycol thioether(Nonionic 218), long chain ethylene oxidepropylene oxide condensationproducts, e.g., Pluronic 61 (molecular weight 1000), polyethylene glycolester of tall oil acids, sodium octyl phenoxyethoxyethyl sulfate, tris(polyoxyethylene) sorbitan monostearate (Tween 60), and sodium dihexylsulfosuccinate.

The solid and liquid formulations can be prepared by any of theconventional procedures. For example, the compounds of the presentinvention can be applied to soil, growing plants, e.g., trees, cottonplants, wheat and other grain plants, vegetable plants, seeds, fabrics,etc., to give pesticidal protection or can be applied to mature cottonbeans, tomatoes, or other leafy plants to give defoliation or desiccantaction.

The biological testing results are compiled in the following tables. InTables 1, 2, 3, 7 and 8 a 0-10 scale is employed with 0 indicating noinhibition and 10 indicating complete inhibition. In Table 4 and thesaprophytic nematode portion of Table 9 the tabulation is expressed aspercent non-motility after a 4 day incubation period. The blank nomotility rate was 10%. In Tables 4, 10 11, 12 and in the desiccationpart of Tables 6 and 13, the 0-10 scale described above was employedwhile the defoliation data in Tables 6 and 13 is given as actual percentdefoliation. In the parasitic nematode part of 'Table 9 the severity ofroot knots on tomato plants planted in soil infested with Meloidogynespp. is indicated on a 0-10 scale where 0 indicates severe knotting and10 indicates freedom from knots.

In the Table the following abbreviations are used:

COL Collectotrichum obiculare FUS Fusarium oxy. f. lycoperseci F. N.Fusarium nivale HEL Helminlhosporium sativum RHIZ Rhizoctonia solaniVERT Verticillium albo-atrum C. ulmi Ceratocystis ulmi PY Pythiumirregulare Ph phytotoxic ppm parts per million lb./A pounds per acre InTables 1 and 7 potato dextrose agar was used in the agar plate tests.

In Table 2 the spore germination tests were carried out with alternariaspp. and Ustilago and the foliage fungicide tests with CollectotrichumObiculare.

The spore germination tests were carried out as follows. A 1 percentsuspension of the compound to be tested in water was prepared and therewas also prequire While ificant C. ulmi 26 Many of the compounds alsoare useful as nematotodes such as Meloidogyne Vcrt inst parasitic nema l,2,Z-trichloroethyldithioethyl-2 '-methyl-4- Rhiz As shown in Tables 5,l0 and 12 the compounds exhibited some post emergent herbicide activitymany of the compounds did not exhibit any sign The compounds were testedas defoliants and desiccants for cotton as shown in Tables 6 and 13. Thecom- As can be seen from Table 3, many of the compounds were extremelyeffective soil fungicides even at the 20. lowest test rates. Because ofthe effectiveness of the in the defoliant-desiccant tests, Compound 6467did In Table 4 and the saprophytic portion of Table 9 the not showdefoliation at the low rates employed in Table compounds were tested asnematocides using water as i I cides aga spp. as shown in Table 9 aswell as against other root knot nematodes. Rates above 200ppm. are replaced on a microscope slide and a film allowed to form 5 for the lessactive compounds- I preemergent herbicide activity several of thecomity.

chlorophenoxy acetate was an outstanding preemergent herbicide.

pounds were applied as a 2 percent solution in acetone at the indicatedrates per acre of cotton plants.

compounds in the primary soil fungicide test in Table 8 some of thecompounds were subjected to a secondary soil fungicide screening.

6 but surprisingly showed very good desiccation. This can be takenadvantage of in Texas and other areas where it is necessary to desiccatecotton prior to pickin g.

TABLE 1.'AGAlt PLATES Organism at p.p.m

Fus I101 25 pared a solution of agar in the water. The suspension 0.3ml. of the agar material was was appropriately diluted with water andmixed w the agar solution to give the indicated concentrations in ppm.

tered, 10 indicating 100 percent non germination in 10 pounds showedexcellent preemergent herbicide activ- The foliage fungicide tests werecarried out with COL infested cucumber leaves.

The soil fungicide tests in Table 3 were carried out with an equalweight of the test compound and atith indicated organism and allowed tostand for 24 hours. Then the blend was spread evenly over a wet Ex. No;

of compounds and solidify. Spores of Alternaria or Ustilago were dustedon the slides and they were placed in' Petri dishes with filter paperand incubated at room temperature for 24 hours and the non germinatedspores regis- Table 2.

tapulgers clay. The mixture was blended with soil infested w paper toweland 50 pea seeds were placed on the soil. The towels were rolled up andput inmetal cans and stored at 40F. for 5 days and then at 75F. for 4days. The cans were then removed and the rate of fungus growth recorded,with 10 indicating no growth.

the medium with Panagrellus and Rhabditis spp. at room temperature. The,less active compounds require rates above 'the 400 ppm. maximum used inTable 9.

Code No.

050008on08 0550 w08mm2 52580 5 005 50000 zoo- 08 M m00m5 mramoo o ow 0011] 0 008 00005 m w wmmm m wm1m wwm wi1 11 1 00 00 05050250000050528200W5X5 l 0 0 5 8 I, J085un5500 l. l 5 0 5005 00405unh5(m0500(050m0w m l1 5 000 05 00 mmmw w m w w 11 1 11 0 l 0 0500008500 mwwwwwlwwwhmmmmwlwl 1111 11 05 M 0 05 mO 080w0m5 m50 58wH5 H0 0008 w mwwmw i w111 00000 .0 800000. mwwmll l1 .1 11111 'lhv higher rate is l000p.p.1n.

TABLE 2.-. I()RE (11C RMINATIUN FOLIAGE FL NUIQHH,

Organism at p.p.m.--

An i un- Cnlldolrichum obiculan:

Code No. EX. N0. 1, 000 100 10 1,000 100 10 1,000 100 10 a 1 0 2 10 3 104 10 6 10 5 7 10 8 8 10 8 3 J 10 5 0 10 5 10 5 U 0 5 0 11 10 5 0 10 0 1210 5 0 10 5 13 8 0 0 5 0 14 0 0 0 0 0 5 0 0 5 0 16 10 5 0 10 0 17 5 0 05 0 18 0 0 0 0 0 1!) 10 5 (l 0 0 10 8 U 10 5 21 0 0 0 10 10 22 10 H 0 105 23 8 0 I) 5 0 2'1 10 H 8 10 10 0 0 U (l 0 20 10 l) (I 10 l) 27 5 n 0 u0 28 H 3 0 8 (I 139 8 '7 l) 8 l) 5 0 (J 5 0 31 10 8 0 10 5 32 5 0 0 0 0TABLE 3.SOIL FUNGICIDE Organism Iy at Fu at Rhiz al \"crt. at-

' 200 500 10 500 100 10 500 100 10 Code No. Ex. No. #/A. #/A. p.p.m.p.p.m. p.p.m. p.p.m. p.p.m. p.p.m. p.p.m. ppm. p.p.m.

1 9 8 10 10 10 10 10 2 10 5) 1O 5 0 10 5 5 0 3 1O 9 1O 5 1O 10 0 4 10 38 8 0 5 0 5 0 6 10 4 10 8 5 10 8 0 0 5 10 8 10 10 8 10 10 1O 1O 7 0 0 1010 0 3 8 7 2 10 5 10 10 10 9 10 e 10 10 10 9 10 3 2 10 0 10 10 b 11 6 58 5 10 5 12 10 6 10 10 8 10 b 13 'J 6 0 0 8 10 14 10 7 1O 0 10 10 15 4 010 0 10 10 t 16 8 5 10 0 10 10 b 17 O 0 10 0 8 1O 5 18 6 2 5 O 10 5 0 197 0 10 0 10 10 5 20 J 6 10 10 10 10 10 21 4 0 0 0 2 5 0 22 8 4 10 10 1010 10 23 6 2 8 0 0 10 10 24 10 7 10 0 10 10 10 25 0 0 10 0 O 5 0 26 J 30 0 8 5 0 27 6 5 0 0 5 0 0 28 10 7 10 8 0 10 10 29 7 6 10 0 10 10 10 306 4 0 0 10 5 0 31 6 4 10 10 10 10 8 32 6 4 8 0 0 10 5 We claim: 1. Acompound having one of the formulae (1) i-ssc nicnon ICE and

(2 )B-SSCH CH OH 5. A compound according to claim 2 which is di totrihalovinyl.

6. A compound according to claim 5 wherein all halogen atoms arechlorine. 5 7. A compound according to claim 6 which is 2,2-

dichlorovinyl-Z',3-dihydroxypropyl disulfide.

8. A compound according to claim 1 having formula 9. A compoundaccording to claim 8 wherein all 10 halogen atoms are chlorine.

10. A compound according to claim 1 which is l ,2,2-trichloroethyl-2,3-dihdyroxypropyl disulfide.

1 l. A compound according to claim 1, which is 2,2,2- 5trichloroethyl-2',3-dihydroxypropyl disulfide.

2. A compound according to claim 1 having formula (1).
 3. A compoundaccording to claim 2 wherein all halogen atoms are chLorine.
 4. Acompound according to claim 3 which is trichloroethyl2''3''dihydroxypropyl disulfide.
 5. A compound according to claim 2which is di to trihalovinyl.
 6. A compound according to claim 5 whereinall halogen atoms are chlorine.
 7. A compound according to claim 6 whichis 2,2-dichlorovinyl-2'',3'' -dihydroxypropyl disulfide.
 8. A compoundaccording to claim 1 having formula (2).
 9. A compound according toclaim 8 wherein all halogen atoms are chlorine.
 10. A compound accordingto claim 1 which is 1,2,2-trichloroethyl-2'',3'' -dihdyroxypropyldisulfide.
 11. A compound according to claim 1, which is2,2,2-trichloroethyl-2'',3'' -dihydroxypropyl disulfide.